EP0400433B1 - Verdoppelte Triphenylmethanfarbstoffe sowie Piperazinderivate - Google Patents
Verdoppelte Triphenylmethanfarbstoffe sowie Piperazinderivate Download PDFInfo
- Publication number
- EP0400433B1 EP0400433B1 EP90109548A EP90109548A EP0400433B1 EP 0400433 B1 EP0400433 B1 EP 0400433B1 EP 90109548 A EP90109548 A EP 90109548A EP 90109548 A EP90109548 A EP 90109548A EP 0400433 B1 EP0400433 B1 EP 0400433B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen
- independently
- alkyl
- different
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 title claims description 16
- 150000004885 piperazines Chemical class 0.000 title claims description 9
- 239000000975 dye Substances 0.000 title description 19
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 title description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- -1 methoxy, ethoxy Chemical group 0.000 claims description 27
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000004040 coloring Methods 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- 150000004698 iron complex Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- YFKCOFBFUSUCSV-UHFFFAOYSA-N 2-(n-ethylanilino)-1-[4-[2-(n-ethylanilino)acetyl]piperazin-1-yl]ethanone Chemical compound C=1C=CC=CC=1N(CC)CC(=O)N(CC1)CCN1C(=O)CN(CC)C1=CC=CC=C1 YFKCOFBFUSUCSV-UHFFFAOYSA-N 0.000 description 1
- DTNQFFYVOVIRFQ-UHFFFAOYSA-N 2-[[2-(dimethylamino)phenyl]methyl]-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1CC1=CC=CC=C1N(C)C DTNQFFYVOVIRFQ-UHFFFAOYSA-N 0.000 description 1
- QYHXZQGNMLVJPX-UHFFFAOYSA-N 2-chloro-1-[4-(2-chloroacetyl)piperazin-1-yl]ethanone Chemical compound ClCC(=O)N1CCN(C(=O)CCl)CC1 QYHXZQGNMLVJPX-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NCMPQWJUQZQHOI-UHFFFAOYSA-N [1-butoxy-3-ethoxy-3-methoxy-2-(2-methylpropoxy)-1-propan-2-yloxy-1-propoxybutan-2-yl] hypofluorite Chemical compound CCCCOC(OCCC)(OC(C)C)C(OF)(OCC(C)C)C(C)(OC)OCC NCMPQWJUQZQHOI-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-M methoxyacetate Chemical compound COCC([O-])=O RMIODHQZRUFFFF-UHFFFAOYSA-M 0.000 description 1
- GUYMMHOQXYZMJQ-UHFFFAOYSA-N n-ethyl-3-methylaniline Chemical compound CCNC1=CC=CC(C)=C1 GUYMMHOQXYZMJQ-UHFFFAOYSA-N 0.000 description 1
- LELNERYBQGXVST-UHFFFAOYSA-N n-ethyl-4-[[4-(ethylamino)-3-methylphenyl]methyl]-2-methylaniline Chemical compound C1=C(C)C(NCC)=CC=C1CC1=CC=C(NCC)C(C)=C1 LELNERYBQGXVST-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
- C09B11/16—Preparation from diarylketones or diarylcarbinols, e.g. benzhydrol
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
- C09B11/18—Preparation by oxidation
Definitions
- DE-A-2 739 953 already discloses doubled triphenylmethane dyes which, for example, have the p-xylylene radical or the piperazine-1,4-diyl radical as a bridge member.
- doubled triphenylmethane dyes which, for example, have the p-xylylene radical or the piperazine-1,4-diyl radical as a bridge member.
- 1,4-bis (chloromethyl) benzene the handling of which is problematic.
- Those dyes which are doubled via a piperazine-1,4-diyl bridge still have defects in their application properties.
- the object of the present invention was therefore to provide new doubled triphenylmethane dyes which can be prepared by means of simple intermediate products and which have favorable application properties.
- R1 represents a C1-C6 alkyl radical which is substituted, e.g. Hydroxy, C1-C4-alkoxy, C1-C4-alkanoyloxy, C1-C4-alkoxycarbonyl, cyano, chlorine, acetyl, acetylamino or phenyl come into consideration.
- R1, R2, R3, R4 and R5 are e.g. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
- R3 and R4 are still e.g. Methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, fluorine, chlorine or bromine.
- R1 are further e.g. Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2 - Formyloxyethyl, 2-acetyloyethyl, 2- or 3-formyloxypropyl, 2- or 3-acetyloxypropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or 3-ethoxycarbonylpropyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 2-chloroethyl, 2- or 3-chloropropyl, but-3-one-1-yl, pent-4-one-1-yl, 2-
- R 1 radicals together with the nitrogen atom connecting them represent a saturated 5- or 6-membered heterocyclic radical, which may optionally have further heteroatoms
- such radicals can, for example, Pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N- (C1-C4-alkyl) piperazino, such as N-methyl or N-ethylpiperazino, come into consideration.
- Suitable anions from which the anion equivalents An ⁇ are derived, are, for example, halide, such as fluoride, choride, bromide or iodide, hydrogen sulfate, sulfate, hydrogen phosphate, phosphate, borate, tetrafluoroborate, trichlorozincate, methosulfate, ethosulfate, benzenesulfonate, o- or p- Toluene sulfonate, methyl sulfonate, formate, acetate, propionate, hydroxyacetate, methoxyacetate or lactate.
- halide such as fluoride, choride, bromide or iodide
- hydrogen sulfate, sulfate hydrogen phosphate, phosphate, borate, tetrafluoroborate
- trichlorozincate methosulfate, ethosulfate, benzenesulfonate
- Triphenylmethane dyes of the formula I in which n denotes 1 are particularly preferred.
- triphenylmethane dyes of the formula I according to the invention can be prepared by methods known per se.
- a piperazine derivative of the formula III in which R4, R5 and n each have the meaning given above, with a Diphenylmethane of the formula IV link in the R1, R2 and R3 each have the meaning given above by means of a catalytic oxidation reaction.
- catalytic oxidation reactions are part of the prior art and are described, for example, in US Pat. No. 3,828,071 or US Pat. No. 4,000 135.
- Another object of the present invention was to provide new piperazine derivatives which are advantageously suitable as intermediates for the synthesis of the triphenylmethane dyes of the formula I.
- the piperazine derivatives of the formula II according to the invention can be prepared, for example, from acylpiperazines of the formula VI by the process described in J. Med. Chem. (Loc. Cit.) in which Hal represents halogen and m has the meaning given above, with anilines of the formula VII in which L1 and L2 each have the abovementioned meaning can be obtained.
- the new piperazine derivatives of the formula II are valuable intermediates for the production of triphenylmethane dyes of the formula I.
- the new triphenylmethane dyes of formula I are violet to reddish blue. They can advantageously be used as basic dyes, especially for dyeing paper. The dyes have a substantial substantivity and largely take off from the aqueous coloring medium; they are therefore very environmentally friendly.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3917601 | 1989-05-31 | ||
| DE3917601A DE3917601A1 (de) | 1989-05-31 | 1989-05-31 | Verdoppelte triphenylmethanfarbstoffe sowie piperazinderivate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0400433A1 EP0400433A1 (de) | 1990-12-05 |
| EP0400433B1 true EP0400433B1 (de) | 1993-11-10 |
Family
ID=6381690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90109548A Expired - Lifetime EP0400433B1 (de) | 1989-05-31 | 1990-05-19 | Verdoppelte Triphenylmethanfarbstoffe sowie Piperazinderivate |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5051504A (da) |
| EP (1) | EP0400433B1 (da) |
| JP (1) | JPH0324166A (da) |
| AU (1) | AU623526B2 (da) |
| CA (1) | CA2016491A1 (da) |
| DE (2) | DE3917601A1 (da) |
| DK (1) | DK0400433T3 (da) |
| FI (1) | FI98145C (da) |
| NO (1) | NO172747C (da) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007296224A (ja) * | 2006-05-02 | 2007-11-15 | Mitsuhiro Kurashige | 組み立て式手足運道具 |
| US9190099B2 (en) * | 2010-03-15 | 2015-11-17 | Purdue Research Foundation | Higher order structured dyes with enhanced optical features |
| JP5221787B2 (ja) | 2011-04-21 | 2013-06-26 | 大日本印刷株式会社 | 色材、及びその製造方法 |
| JP5813561B2 (ja) * | 2011-04-21 | 2015-11-17 | 大日本印刷株式会社 | 色材、及びその製造方法 |
| US9708244B2 (en) * | 2012-10-18 | 2017-07-18 | Dai Nippon Printing Co., Ltd. | Coloring material and method for producing the same |
| TWI550030B (zh) * | 2012-10-19 | 2016-09-21 | 大日本印刷股份有限公司 | 色材及其製造方法 |
| JP6424068B2 (ja) * | 2014-11-06 | 2018-11-14 | 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． | 化合物 |
| JP6255634B1 (ja) * | 2016-02-25 | 2018-01-10 | Dic株式会社 | 化合物及びカラーフィルタ |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1481016A (fr) * | 1962-04-02 | 1967-05-19 | Bruneau & Cie Lab | Dérivés de la pipérazine et leur fabrication |
| GB1051527A (da) * | 1964-07-31 | |||
| DE1570013B1 (de) * | 1964-07-31 | 1970-07-02 | Kyorin Seiyaku Kk | 1,4-Bis-(phenoxyacetyl)-piperazinderivate und Verfahren zu ihrer Herstellung |
| US3763166A (en) * | 1967-12-29 | 1973-10-02 | Ciba Geigy Corp | N,n'-bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)lower alkanoyl)piperazines |
| BE787210A (fr) * | 1971-08-04 | 1973-02-05 | Basf Ag | Procede pour l'oxydation catalytique de composes di- et tri-(hetero)-aryl-methanes |
| US4000135A (en) * | 1973-07-10 | 1976-12-28 | Basf Aktiengesellschaft | Manufacture of basic dyes by catalytic oxidation |
| DE2739953A1 (de) * | 1977-09-05 | 1979-03-22 | Basf Ag | Verdoppelte triphenylmethanfarbstoffe |
| DE2928404A1 (de) * | 1979-07-13 | 1981-01-29 | Bayer Ag | Verfahren zur herstellung basischer farbstoffe |
-
1989
- 1989-05-31 DE DE3917601A patent/DE3917601A1/de not_active Withdrawn
-
1990
- 1990-05-10 CA CA002016491A patent/CA2016491A1/en not_active Abandoned
- 1990-05-10 US US07/521,382 patent/US5051504A/en not_active Expired - Fee Related
- 1990-05-19 DE DE90109548T patent/DE59003404D1/de not_active Expired - Fee Related
- 1990-05-19 DK DK90109548.9T patent/DK0400433T3/da active
- 1990-05-19 EP EP90109548A patent/EP0400433B1/de not_active Expired - Lifetime
- 1990-05-24 FI FI902588A patent/FI98145C/fi not_active IP Right Cessation
- 1990-05-29 AU AU56090/90A patent/AU623526B2/en not_active Ceased
- 1990-05-30 NO NO902392A patent/NO172747C/no unknown
- 1990-05-30 JP JP2138641A patent/JPH0324166A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FI902588A0 (fi) | 1990-05-24 |
| AU623526B2 (en) | 1992-05-14 |
| NO172747C (no) | 1993-09-01 |
| NO902392D0 (no) | 1990-05-30 |
| DK0400433T3 (da) | 1993-12-20 |
| US5051504A (en) | 1991-09-24 |
| FI98145C (fi) | 1997-04-25 |
| JPH0324166A (ja) | 1991-02-01 |
| CA2016491A1 (en) | 1990-11-30 |
| NO902392L (no) | 1990-12-03 |
| AU5609090A (en) | 1990-12-06 |
| FI98145B (fi) | 1997-01-15 |
| DE3917601A1 (de) | 1990-12-06 |
| DE59003404D1 (de) | 1993-12-16 |
| NO172747B (no) | 1993-05-24 |
| EP0400433A1 (de) | 1990-12-05 |
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